第 13 章 新催化材料
DESCRIPTION
第 13 章 新催化材料. 一、金属碳化物及氮化物. 金属碳化物 / 氮化物具有类贵金属的催化性能。. 1.1 金属碳化物和金属氮化物的结构. 金属原子组成 fcc 、 hcp 、 hex 晶格结构,碳原子和氮原子位于金属原子晶格的间隙位置。这种结构的化合物称为间充化合物。金属碳化物或氮化物结构由其几何因素及电子因素决定: 1 )几何因素 -H äag 经验规则 :非金属原子与金属原子的球半径比小于 0.59 时,就会形成简单的 fcc 、 hcp 、 hex 晶体结构; - PowerPoint PPT PresentationTRANSCRIPT
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13 1.1 fcchcphex1-Hag0.59fcchcphex2-Engel-Brewers-ps-pbcchcpfccMo(bcc)-Mo2C(hcp)-Mo2N(fcc)/
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1.2 CNdVIII12FTC2-C43CONH3NO4HDNHDS
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1.3 1 M + 2CO MC + CO2 MO + NH3 MN + H2O + H22 W(CO)n + HxCy WC + H2O + CO Ti(NR2)4 + NH3 TiN + CO + H2O3 MoO3 + CH4 + H2 Mo2C + 3H2O WO3 + NH3 W2N + H2O
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4 Mo(CO)6/Al2O3 Mo2C/Al2O3 TiO2/SiO2 + NH3 TiN/SiO25 V2O5(g) + C VC + CO6 MoCl4(THF)2 + LiB(Et)3H Mo2C [(Me)3SiN]3La + NH3 LaN
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1.4 1-Mo2N0.78
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2Mo2N
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3Mo2ChcpMo2CfccCO1 Mo2ChcpMo2CfccMoO3H2MoCH4/H2Mo2ChcpMoO3NH3Mo2NfccMo2NfccCH4/H2Mo2Cfcc2 Mo2ChcpMo2CfccCOMo2Chcp50min16hMo2Cfcc50min250min
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4Mo2ChcpMo2CfccC2H6Mo2ChcpMo2Cfcc200Mo2Chcp101Mo2Cfcc200
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2.1 1M-P12NaH2PO2Ni-PCo-PNi-Co-PRu-PNi-W-PNi-Pd-P2M-BKBH4Ni-BCo-BFe-BRu-BPd-BNi-M-B
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2.2 1NiBNi/Al2O3NiB/SiO2
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LH Ni
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2NiB/SiO21NiB/SiO2---Ni80P20
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2Pd/Al2O333%70%
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N2NiB/SiO2
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3COPd33Zr67Pd/ZrO2Pd/ZrO2
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3.1 d+DSl-LRDLDNA
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3.2 3.3 1ee2yo[]m[]p
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3.4 1
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23.5 1--
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D10PPh/DIPAMPL-dopa
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R-BINAP
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2
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3C-C
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3.6 RhRhNiUSYN-
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4.1 1-100 nm4.2 12
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34
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4.3
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4.4 1
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2MTG
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3
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4NiO7-10nmNiO275NiO400
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5H3PW12O40/SiO230-50nmH3PW12O40/SiO240nm218.9m2/g
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6
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Nanoparticles/thin oxide film/metal substrate model catalysts---case 1. Au/TiO2(110)Goodman et al. Science 281 (1998) 1647Haruta et al. J. Catal. 144 (1993) 175
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Goodman et al. Science 306 (2004) 252
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Structure-controllable nanoparticles catalysts---case 1. shape effect of Pt NCs on the catalytic activityTian & Sun et al. Science 316 (2007) 732
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Tian & Sun et al. Science 316 (2007) 732
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Structure-controllable nanoparticles catalysts---case 2. catalysis by confined nanoparticlesPan & Bao et al. Nat. Mater. 6 (2007) 507
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Pan & Bao et al. Nat. Mater. 6 (2007) 507
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Structure-controllable nanoparticles catalysts---case 3. shape effect of oxides on catalysisLi et al. J. Catal. 229 (2005) 206
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1.5-10nm700m2/g5.1 1MCM41LCTMCM-41
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DavisMCM41MCM-41
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StuckyMCM41
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2-MobileG=V/A0LVA0LG=1/31/2 G=1/22/3G1
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StuckyS+I-I-S+I-S-I+S+X-I+/S-X+I-XS0I0S-I
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5.2 1TiZrVCrMoWMn-- WO3Fe2O3PbOZrO2Al2O3TiO2VPOAlPO4 2
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X-EDXBETTPD3
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5.3 1Na-MCM-41Cs-MCM-41MCM-41-
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2MCM-413-
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6.1 CO1Pt-CoOx/Al2O3Pd-Ce/Al2O3Au/MOx23Pdn/YAu/MCM-41Cu/TS6.2 1C-H393K6atmH2PtCl6/Na2PtCl4
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PdHg2+Hg(OSO3H)2373K1.8MPaCH3HgOSO3H
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2BassetZrTiHf423K
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6.3 DMCCaODMC
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6.4 Au-Pt/Co3O4